Amino substituted 1,2,4-triazinones

ABSTRACT

Compounds having the structural formula   WHEREIN R is methyl, ethyl, furfuryl,   IN WHICH R1 is hydrogen or methyl; R2 is phenyl, acetyl or propionyl when R1 is hydrogen and R2 is methyl when R1 is methyl; R3 is hydrogen or C1-C6 alkyl; R4 is C1-C6 alkyl, phenyl or C1-C3 carboalkoxy; and R5 is hydrogen or C1-C6 alkyl. The compounds are useful for inhibiting the upright growth of cool season turfgrasses and some monocot weed species found with turfgrasses.

United States Patent 1 1 Wittenhroolr [54] AMINO SUBSTITUTED 1,2,4-TRIAZINONES [75] Inventor: Lawrence S. Wittenbrook,

Marysville, Ohio [73] Assignee: O. M. Scott & Sons Company [22] Filed: June 22, 1973 [21] Appl. No.: 372,599

[52] US. Cl. 260/248 AS; 71/93 [51] llnt. Cl C07d 55/10 [58] Field of Search 260/248 AS [56] References Cited UNITED STATES PATENTS 6/1964 Burch 260/248 OTHER PUBLICATIONS Guo et al., Chemical Abstracts, Vol. 61 entry 565ld (1964). Matolscy et 211., Chemical Abstracts, Vol. 69, entry Primary Eraminer-John M. Ford Attorney, Agent, or Firm-James B. Raden; Harold J.

Holt

[57] ABSTRACT Compounds having the structural formula [111 ;'-3,879,386 [451 Apr. 22, 1975 wherein R is methyl, ethyl, furfuryl,

in which R is hydrogen or methyl;

R is phenyl, acetyl or propionyl when R is.

10 Claims, No Drawings AMTNO SUBSTITUTED 1,2,4-TRIAZINONES wherein R is methyl, ethyl, furfuryl,

in which R, is hydrogen or methyl; R is phenyl, acetyl or propionyl when R, is hydrogen and R is methyl when R, is methyl; R is hydrogen or C C alkyl; R, is C, -C is alkyl, phenyl or C, C;, carboalkoxy;

and R is hydrogen or C -C alkyl. The compounds of the present invention are particularly useful for inhibiting the upright growth of cool season trufgrasses and some monocot weed species found with turfgrasses.

Examples of compounds falling within the scope of the above formula are l. S-furfurylarninol ,2,4-triazin-3(2H )-one 2. 5-methylamino'l ,2,4-triazin-3(2H)-one 3. 5-( 2 -phenylhydrazino)-l ,2,4-triazin-3 2H )-one 4. 5-(2,2'-dimethylhydrazino)-1,2,4-triazin- 3( 2H )-one 5. 5-( 2'-acetylhydrazino l ,2,4-triazin-3(2H)-one 6. 5-(2-isopropylidenehydrazino)-1,3,4-triazin- 3( 2H)-one 7. 5-(2-ethylpyruvalidene hydrazino)-l,2,4-triazin- 3(2H)-one 8. 5-(2'-tridecyli-7-denehydrazino)-l ,2,4-triazin- 3(2H)-one 9. 5-(2-( 3"-methylcyclohexylidene)hydrazino)-l ,2,4-

triazin-3( 2H )-one The compounds of the present invention may be prepared by reacting 6-azauracil (l,2,4-triazin-3,5dione) with phosphorous pentasulfide to produce the thio de- 5 rivative 4-thio-6-azauracil. The thio derivative is then reacted with the appropriate amine or hydrazine in the presence of a suitable solvent, such as a low molecular weight alcohol to produce compounds where R is methyl, ethyl furfuryl or For example, the preparation of 5'methylaminol,2,4-triazin-3(2H)'-one is illustrated by the following equation:

N-H Pyridine H l Pass N (H20) T/ fi-azauracil SI NRCHa A N-H Alcohol N i HaNHz N N t \N \N a 1i 4-thiofi-azauracil 5-methy1amino 1,2,4-

triazin-3(2H)-one The preparation of S-hydrazino-l,2,4-triazin-(2H)-one would be as set forth above except that hydrazine would replace methyl amine. Compounds in which R is -N or -N= E \R4 would require further reaction of the aforementioned hydrazine derivatives with an aldehyde or ketone in the presence of a suitable solvent, such as ethanol, and a suitable acid catalyst, such as acetic acid, as exemplifled in the following equation:

The following examples illustrate the preparation of compounds within the scope of the present invention:

EXAMPLE 1 The thio derivative of 6-azauracil was prepared as follows: To a vigorously stirred mixture of 6-azauracil, 8.0g (71 m mole), in 250 ml. pyridine and ten drops of water was cautiously added phosphorous pentasulfide, 7.5g. (34 m mole). The reaction mixture was refluxed for three hours. Removal of solvent in vacuo afforded a residue which was dried over phosphorous pentoxide in vacuo. This material was slurried in water, treated with sodium hydroxide solution n 9 and filg ifgj f i tered. Acidification (pH 3) of the filtrate with cone. hy- I'D-one as a yellow m p pure drochloric acid solution gave a precipitate which was F P of y extracted with ethyl ether. The combined ether exgi was @9 9 as a yellow m tracts were washed with water, dried over magnesium p 6 C by recrystalhzduon from ethano l5 Calcd. for C H N O: C, 43.11.; H, 5.43: N, 41.89. sulfate, filtered, and evaporated m vacuo to give 8.5g.

Found: C, 42.90; H, 5.95; N, 41.30. A 1648 (94%) of 4-th1o-6-azaurac1l as an orange solid, mp 1588 C=O 3250 2800 N H 219-22l. An infrared spectrum of the crude material 7 cm compared with that of authentic 4-thio-6-azauracil. EXAMPLE 3 The following is a typical procedure for the prepara- Additional compounds within the scope of the invention of an amino derivative of the invention, in this case tion were prepared substantially similarly to Examples S-furfurylamino-l,2,4-triazin-3-one, by reaction of the l and 2. The melting points and calculated v found foregoing thio compound with furfurylamine. To a chemical content of the compounds are set forth in the stirred slurry of 4-thio-6-azauracil, 7.8g. (0.06 mole), following table. The numbers of the compounds correin 75 ml. n-propanol was added dropwise furfuryla- 'spond to those set forth in the specification above.

Com- M.p., C Formula C H N pound l 25 l .5-253.5 CNHKN4OZ Calcd 50.00 4.19 29.16 Found 50.00 4.10 29.19 2 300 C4H6N4O Calcd 38.09 4.79 44.43 Found 3832 5.17 44.42 3 2489 C,,H9N,,O Calcd 53.20 4.46 34.47 Found 53.50 4.21 34.21 4 244-6 C,,H,N ,o Calcd 38.70 5.85 45.14 Found 37.65 6.15 44.67 5 245-6 C H N O2 Calcd 35.50 4.17 41.41 Found 35.50 4.14 41.50 6 216-8 CGHQNSO Calcd 43.1 1 5.43 41.89 Found 42.90 5.95 41.30 7 188--191 C,.H"N5O3.H2O Calcd 39.50 5.39 28.80

Found 39.43 5.36 29.17 I *8 C,,,H ,,N O Calcd Found 9 64-4 C H N O Calcd 54.29 6 83 31.65 Found 54.15 7.27 31.27

Because of difficulties in analyzing this compound, spectral data were relied upon to establish structure.

mine, 17.5g. (0.18 mole), over a period of 35 minutes (mildly exothermic) at room temperature. When the addition was completed, the reaction mixture was stirred overnight 18 Hr.) at ambient temperature. The

pale yellow precipitate was filtered, washed with water, and dried; 6.9g. (52%), m p 245.5-248 (uncor.). Recrystallization from etahnol-water (ca 1:1) afforded pure S-furfurylamino-l,2,4-triazin-3(2H)-one, m p 251.5-253.5C.

Calcd. for C H N O C, 40.74; H, 4.17; N, 29.00. Found: C, 50.00; H, 4:09; N, 29.20. A 3.17, 3.22p.(N-H); 6.02, 6.33, 6.5011. (C=O, ring vibrations) EXAMPLE 2 This example illustrates a typical preparation of a compound in which R is by further reaction of S-hydrazino-l,2,4-triazin- 3(2H)-one, prepared as in Example 1 except that hy- I claim: 1. A compound having the structural formula 4. 5-(2'-phenylhydrazino)-1,2,4-triazin-3(2H)-one.

5. 5-2, 2"-dimethylhydrazino)-1,2,4-triazin- 3(2l-l)-one.

6. 5-(2'-acetylhydrazino)- l ,2,4-triazin-3 2H )-one.

7. 5-(2'-isopropylidenehydrazino)-1,2 ,4-triazin- 3(2H)-one.

8. 5-(2-ethylpyruvalidene hydrazino)-1,2,4-triazin- 3-(2H)-one.

9. 5-(2'-tridecyli 7-denehydrazino) 1,2,4-triazin-3- (2l-l)-one.

l0. 5-(2'-3-methylcyclohexylidene) hydrazino) l,2,4-triazin-3(2l'l)-one. 

1. A COMPOUND HAVING THE STRUCTURAL FORMULA 3-(O=),5-(R-NH-)-2,3-DIHYDRO-1,2,4-TRIAZINE WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF ETHYL, METHYL, FURFURYL R1-N(-R2)-, R3-C(-R4)=N-, AND (R5-CYCLOHEXYLIDENE)=N-, IN WHICH R1 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND METHYL, R2 IS SELECTED FROM THE GROUP CONSISTING OF PHENYL, ACETYL AND PROPIONYL WHEN R1 IS HYDROGEN AND R2 IS METHYL WHEN R1 IS METHYL,R3 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND C1-C6 ALKYL, R1 IS SELECTED FROM THE GROUP CONSISTING OF C1-C8 ALKYL, PHENYL AND C1-C8 CARBOALKOXY, AND R5 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND C1-C8 ALKYL.
 1. A compound having the structural formula
 2. 5-furfurylamino - 1,2,4-triazin-3(2H)-one.
 3. 5-methylamino - 1,2,4-triazin-3(2H)-one.
 4. 5-(2''-phenylhydrazino)-1,2,4-triazin-3(2H)-one.
 5. 5-2'', 2''''-dimethylhydrazino)-1,2,4-triazin-3(2H)-one.
 6. 5-(2''-acetylhydrazino)-1,2,4-triazin-3(2H)-one.
 7. 5-(2''-isopropylidenehydrazino)-1,2,4-triazin-3(2H)-one.
 8. 5-(2''-ethylpyruvalidene hydrazino)-1,2,4-triazin-3-(2H)-one.
 9. 5-(2''-tridecyli - 7-denehydrazino) - 1,2,4-triazin-3-(2H)-one. 